A new stereoselective approach to aminocyclohexitols using a Grignard addition on to an N-benzyl sugar imine and RCM

A new stereoselective approach for the synthesis of cyclohexitols using a Grignard addition on to an N-benzyl sugar imine and RCM from d-glucose has been described; the glycosidase inhibitory activity of these amino cyclohexitols has also been studied.

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(S)-N-Benzyl-1-((3aR,5R,6R,6aR)-6-(benzyloxy)-2,2-dimethl-6-vinyl-tetrahydrofuro[2,3-d][1,3]dioxol-5yl)but-3en-1-amineC27H33NO4[α]D30=+47.1 (c 1.46, CHCl3)Source of chirality: d-glucoseAbsolute configuration: (S,3aR,5R,6R,6aR)

Benzyl benzyl ((S)-1-(3aR,5R,6R,6aR)-6-(benzyloxy)-2,2-dimethyl-6-vinyl-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl)but-3-enyl)carbamateC35H39NO6[α]D30=+20.6 (c 2.29, CHCl3)Source of chirality: d-glucoseAbsolute configuration: (S,3aR,5R,6R,6aR)

Benzyl benzyl ((S)-1-(2R,3S,4R)-3-(benzyloxy)-4,5-dihydroxy-3-vinyltetra hydrofuran-2,-yl)but-3-enyl)carbamateC32H35NO6[α]D30=+32.9 (c 0.77, CHCl3)Source of chirality: d-glucoseAbsolute configuration: (S,2R,3S,4R)

Benzyl benzyl ((4S,5R,6S)-6-(benzyloxy)-,5-hydroxy-6-(hydroxymethyl)octa-1,7-dien-4-yl)carbamateC31H35NO5[α]D30=+245.7 (c 1.52, CHCl3)Source of chirality: d-glucoseAbsolute configuration: (4S,5R,6S)

(4S,5R)-4-Allyl-3-benzyl-5-((S)-2-(benzyloxy)-1-hydroxybut-3en-2-yl)oxazolidin-2-oneC24H27NO4[α]D30=-6.1 (c 2.0, CHCl3)Source of chirality: d-glucoseAbsolute configuration: (4S,5R,S)

(4S,5R)-4-Allyl-5-((S)-1,2-hydroxybut-3en-2-yl)oxazolidin-2-oneC10H15NO4[α]D30=-37.5 (c 0.48, MeOH)Source of chirality: d-glucoseAbsolute configuration: (4S,5R,S)

(3aS,7S,7aR)-7-Hydroxy-7-(hydroxymethyl)-3a,4,7,7a-tetrahydrobenzo[d]oxazol-2(3H)-oneC8H11NO4[α]D30=+101.8 (c 0.77, MeOH)Source of chirality: d-glucoseAbsolute configuration: (3aS,7S,7aR)

(3aS,4′S,7aR)-2′,2′-Dimethyl-3,3a,4,7a-tetrahydro-2H-spiro[benzo[d]oxazole-7,4′-[1,3]dioxolan]-2-oneC11H15NO4[α]D30=+68.0 (c 1.3, CHCl3)Source of chirality: d-glucoseAbsolute configuration: (3aS,4′S,7aR)

(3aS,4′R,5S,6S,7aR)-5,6-Dihydroxy-2′,2′-dimethylhexahydro-2H-spiro[benzo[d]oxazole-7,4′-[1,3]dioxolan]-2-oneC11H17NO6[α]D30=-6.8 (c 0.5, CHCl3)Source of chirality: d-glucoseAbsolute configuration: (3aS,4R,5S,6S,7aR)

(1R,2S,3S,4S,6S)-6-Amino-2-(hydroxy methyl)cyclohexane-1,2,3,4-tetraolC7H15NO5[α]D30=+27.2 (c 0.2, H2O)Source of chirality: d-glucoseAbsolute configuration: (1R,2S,3S,4S,6S)

(1S,2R,3S)-3-Amino-1-(hydroxymethyl)cyclohexane-1,2-diolC7H15NO3[α]D30=+47.3 (c 0.2, H2O)Source of chirality: d-glucoseAbsolute configuration: (1S,2R,3S)